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  • 1990-1994  (688)
  • 1955-1959
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  • 1992  (688)
  • Chemical Engineering  (688)
  • 1
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A study of simultaneous acoustic and rheometric (dynamic mechanical) measurements of the epoxy curing process is undertaken to assess the validity of using acoustic cure-monitoring sensors for process control. Our results demonstrate that the acoustic technique provides a sensitive means for monitoring the cure of neat epoxy over the entire cure cycle. The acoustic modulus calculated from the shear velocity qualitatively tracks the mechanically measured dynamic modulus and correctly ranks the stiffness of two epoxy compositions. When the frequency difference is accounted for, using time-temperature superposition of the dynamic mechanical measurements, quantitative agreement between the acoustic and mechanical moduli for fully cured epoxy resins is also quite good.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 32 (1992), S. 467-474 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The grafting of maleic anhydride (MAH) on high density polyethylene in a counter-rotating twin screw extruder has been studied. As the reaction kinetics appear to be affected by mass transfer, good micro mixing in the extruder is important. Due to the competing mechanisms of increasing mixing and decreasing residence times at increasing screw speed, and due to the complicated reaction scheme, various non-linearities exist that are prohibitive for simple optimization rules. The interaction diagram presented in this paper for a twin screw extruder as a MAH grafting reactor can be used for better understanding of the influence of the extruder parameters on the reaction process.
    Additional Material: 9 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 32 (1992), S. 488-493 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Gear pump assisted extrusion is becoming popular in the plastics processing industries. The growth has been tremendous since 1980. In this study, the benefits of gear pump assisted extrusion, especially in single screw applications, is critically reviewed, and a method of predicting the operational conditions of the gear pump assisted extrusion system is discussed. Further, shortening the length to diameter ratio of the extruder in gear pump assisted extrusion was analyzed and found to produce a reduction in energy consumption, provided melting is completed.
    Additional Material: 4 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 32 (1992) 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 32 (1992), S. 506-515 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Internal stresses in injection-molded parts are the result of thermal, flow, and pressure histories. Internal stresses can be roughly divided into thermal and flow-induced stresses. In this paper, a modified layer-removal method is presented to determine thermal stress distributions in injection-molded flat plates. With this method, the curvature of a rectangular specimen is determined after the removal of a layer from one surface. This curvature is converted into a stress via a mathematical relation, originally derived by Treuting and Read. By determining the local curvatures after successive layer removals, stress distributions along the flow path were obtained within a single specimen. Validation of this modified layer-removal method is described. A good reproductibility was obtained. The method can be regarded as semi-quantitative. Flat plates were injection-molded from three amorphous polymers: polystyrene, polycarbonate, and a polyphenylene ether/high-impact polystyrene blend. In general, the flat-plate cross-section shows a three-region stress distribution with a tensile stress region both at the surface and in the core of the flat plate and an intermediate region with compressive stresses. The modified layer-removal method was used to determine influences of mold temperature, annealing treatment, and pressure history on the thermal stress distributions. Increasing mold temperature results in a decreasing overall stress level, while the compressive stress region shifts to the surface. An annealing treatment significantly reduces the overall stress level, without affecting the stress pattern. Stress distributions along the flow path were influenced by the varying pressure histories from the entrance to the end of the mold cavity. The various features of the stress profiles are explained by the influence of the pressure decay rate in the injection-molding process.
    Additional Material: 20 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 32 (1992), S. 529-534 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The network formation processes for imidazole-cured epoxy resins were examined by relating the reaction chemistry and the physical properties during cure. Network formation models were developed based on kinetic studies and the laws of conditional probability. These models were used to predict the weight-average molecular weight, the gel point, and the sol fraction as a function of the resin composition and the processing conditions. Rheological and extraction experiments were conducted to confirm the model results and to develop criteria for identifying the gel point.
    Additional Material: 5 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 32 (1992), S. 535-541 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The kinetics of cyclotrimerization and the thermal stability of bisphenol Abased cyanate ester resin systems were determined using Fourier transform infrared spectroscopy, differential scanning calorimetry, and thermogravimetry. The bisphenol A dicyanate was cured with 4 phr nonylphenol and with the octoates of zinc and manganese, and cobalt acetylacetonate at concentrations ranging from 0 to 750 ppm metal. An empirical rate law was used to predict the cyanate concentration profiles. The observed reaction rate showed a first-order dependenće on the initial metal concentration and a second-order dependence on the cyanate concentration in the kinetically controlled regime. For the uncatalyzed systems, the kinetics was described by a second-order autocatalytic model. The thermal stability of the network was found to be dependent on the catalyst concentration for the zinc catalysts. For the samples cured with manganese, no effect of concentration on the thermal stability was observed.
    Additional Material: 10 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 32 (1992), S. 558-566 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Ar+ irradiation and annealing at an elevated temperature are used to improve the adhesion of deposited Cr thin films by vacuum evaporation onto polyimide (PI) substrates. The Ar+ ions of 50 and 200 keV and various Ar+ doses ranging from 1 × 1013 to 2 × 1016 ions/cm2 are chosen for the experiments, after many preliminary trials. The surface analyses are conducted employing Rutherford Backscattering Spectroscopy (RBS), Fourier transform infrared spectrometry (FTIR), X-ray photoelectron spectroscopy (XPS), and Scanning electron microscopy (SEM). Ar+ irradiation produces an interfacial layer of about 100 Å (10 nm) thick in which Cr particles and PI molecules are physically mixed and chemically bonded. The chemical bonds of Cr—O and a trace of Cr≡C are observed by XPS and FTIR. Impact-wear tests are also conducted in order to determine the effects of the Ar+ irradiation on the wear property of a Cr/PI system. A significant increase in the property is observed and the increase appears to be a function of the degree of adhesion of the Cr film to the PI substrate.
    Additional Material: 12 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 32 (1992), S. 581-581 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 32 (1992), S. 582-585 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Deep penetration welding of polymers can be carried out at high speed with relatively low laser power. This results from an efficient coupling CO2 laser radiation to polymers that leads to volume heating. A brief review of energy coupling and heat transfer effects in polymers under CO2 laser welding conditions is given. Some examples of low power (10 to 100 watt) CO2 welding of polypropylene and polyethylene at depths of up to 1.5 cm are discussed.
    Additional Material: 5 Ill.
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  • 11
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 32 (1992) 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Type of Medium: Electronic Resource
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  • 12
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 32 (1992), S. 206-212 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Coat-hanger dies are commonly used for the extrusion of plastic sheets and films. To describe the flow of a molten polymer through a coat-hanger die, a two-dimensional approach is necessary. Moreover, the thermal effects, which play an important role in the flow distribution, have to be taken into account. In this paper, two numerical models for the simulation of coat-hanger dies are described and compared. These models differ mainly in the simplifying assumptions used and in the treatment of the thermal problem. The simulations obtained with the two models were compared with each other and with experimental data. The discrepancies between the two models can be explained by the different theoretical treatments.
    Additional Material: 17 Ill.
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  • 13
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 32 (1992), S. 213-220 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A general computation of multilayer coextrusion flow in a flat die geometry is presented. For any given number of layers of different polymers, characterized by their thermal and rheological behaviors, the model permits computation of velocity and temperature fields along the flow in constant or slightly varying geometries. The influence of different operating parameters (wall regulation temperature, flow rate, initial temperatures) on the interface positions and temperature evolutions is evaluated. Theoretical predictions of interface positions are in agreement with experiments carried out on an industrial multimanifold flat die.
    Additional Material: 15 Ill.
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  • 14
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 32 (1992), S. 221-230 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A critical part of any master model used to simulate or control a composite material manufacturing process is the description of resin flow through the fiber bed. We present here a review of both theoretical and experimental studies of fluid flow through porous media, including fiber beds. For the practical porosity range of interest in continuous fiber composites processing (0.3〈 ∊ 〈 0.6), the permeability cannot be accurately described using the Blake-Kozeny-Carman equation, even though the flow is Newtonian at very low Reynold's number. For aligned fiber situations, the Kozeny constant, k, deviates radically from theory, depends on bed nonuniformities, and is only constant over very narrow porosity ranges. Thus, one cannot experimentally determine k at high porosities and use this value to describe low porosity situations. Theoretical attempts, based on perfectly spaced and aligned arrays of cylinders, adequately describe the transverse permeability of ideal fiber beds in the high porosity range, but do not succeed at porosities below 0.6. For axial flow through aligned fiber beds, the theory yields permeabilities much lower than are experimentally observed throughout the entire porosity range. For randomly arranged fibers, random cylinder theory also predicts permeabilities that are significantly lower than are measured.
    Additional Material: 4 Ill.
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  • 15
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 32 (1992), S. 240-253 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A method is presented for measuring three-dimensional fiber orientation in fiber-reinforced polymers and placing confidence limits on the results. The orientations of individual fibers are determined from the elliptical intersections between the cylindrical fibers and a polished section. This can be done using either manual digitization or automated image analysis. Volume averages for the sample are computed using an orientation-dependent weighting function that corrects for the bias of an area-based sample. Equations are developed for nonuniform fiber lengths, using both number-average and weight-average measures of orientation. Sources of systematic, measurement, and sampling error are discussed and equations for sampling error and the propagation of measurement error are derived. The results use a second-rank tensor to characterize fiber orientation, but the error analysis can be applied to any type of orientation parameter. We implement the technique using manual digitization of optical micrographs. Our implementation accurately measures samples with known orientation, and produces identical results from two perpendicular sections of a glass fiber/nylon injection-molded sample.
    Additional Material: 10 Ill.
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  • 16
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 32 (1992), S. 273-279 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: We have studied the impact strength, by Charpy and Izod tests, of blends of polyamide 6 with different rubbers, 10 wt% of each, or rubbers and glass fibers (8.5 wt% and 15 wt% respectively). The rubbers are from three different families: (i) a nonreactive cross-linked terpolymer, methyl methacrylate/butadiene/styrene (17/64.5/18.5); (ii) two block copolymers compatible with the matrix, poly(tetramethylene glycol)/polamide 12 (70/30 or 34/66); and (iii) two polymers containing reactive functionality, a terpolymer ethylene/ethyl acrylate/maleic anhydride (68/30.5/1.5) and a copolymer ethylene/acrylic acid (90/10). The classification of additives in regard to improved impact depends on the procedure used for the impact strength measurement, particularly on whether the samples are notched or unnotched. The results are discussed in relation to the dimensions and the adhesion of the rubber particles. The level of adhesion has been estimated from observations in scanning electron microscopy of cavities due to pullout nodules and of nonextracted rubber after treatment in boiling xylene. Strong variations in the morphologies are found, depending on the chemical nature of the rubber. The crystalline state of the polyamide in the blends has also been evaluated from differential scanning calorimetry.
    Additional Material: 9 Ill.
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  • 17
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 32 (1992), S. 287-297 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Sheet composites of polypropylene and poly(ethylene terephthalate) were produced by melt consolidation of alternating layers of polymer films and random glass fiber mats. The composites had a nominal glass content of 50 wt% (∼30 vol%). The sheets were stamped into a complex part from which test specimens were machined, and mechanical properties determined. Flexural strengths as high as 159 MPa were recorded for polypropylene composites and 313 MPa for poly(ethylene terephthalate) composites. The flexural modulus of the polypropylene composites reached 9.1 MPa, whereas the modulus of the stiffest poly(ethylene terephthalate) composite was 15 GPa. The impact properties of the composites were equally high. Polypropylene composites absorbed up to 257 J/cm during an instrumented falling dart impact test. Poly(ethylene terephthalate) composites absorbed as much as 116 J/cm in the same test.
    Additional Material: 14 Ill.
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  • 18
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 32 (1992) 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Type of Medium: Electronic Resource
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  • 19
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 32 (1992), S. 298-304 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The fiber straightening pre-tension applied during the sample preparation of single fiber composites is suggested here to significantly affect the number of fragments as well as the value of the Kelly-Tyson interface shear strength obtained from single filament composite tests. This implies that fragmentation tests performed under seemingly identical conditions, but in which the fiber pre-tension is not accurately controlled during sample preparation, might yield widely differing experimental results. We present and discuss a new set of experimental results dealing with fiber pre-tension effects in carbon/epoxy single fiber composites.
    Additional Material: 8 Ill.
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  • 20
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Surface-induced transcrystallization in fibers has been reported in some advanced polymer composites. It is believed that transcrystalline interphase may affect stress transfer efficiency between the reinforcing fiber and the matrix. In this study, attempts were made to examine the effects of transcrystallinity on composite performance, particularly on fiber-matrix interfacial bond strength, and to investigate possible attributes of transcrystallization. Three polymer resins, poly(etherketoneketone) (PEKK), poly(etheretherketone) (PEEK), and poly(phenylenesulfide) (PPS), and four types of fiber, polyacrylonitrile (PAN)-based AU-4 (untreated AS-4) carbon, pitch-based carbon, poly (p-phenylene terephthalamide) (PPDT) aramid, and E-glass were used. It was found that PPDT aramid and pitch-based carbon fibers induce a transcrystalline interphase in all three polymers because of an epitaxial effect. Under certain conditions, transcrystallization was also observed in PAN-based carbon and E-glass fibers, which may be partially attributed to the thermal conductivity mismatch between the fiber and the matrix. Plasma treatment on fiber surface showed a negligible effect on inducing transcrystallization, whereas solution-coating of PPDT on the fiber surface showed a positive effect. The Microdebonding test, which measures the interfacial bond strength between the fiber and the matrix, consistently showed more than 40% increments for various single filament systems with transcrystalline interphase versus without. However, the effects of transcrystallinity on the interfacial bond strength appeared to decrease as the fiber content increased in composites.
    Additional Material: 7 Ill.
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  • 21
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 32 (1992), S. 475-480 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: An approach to formulation is presented that is based on a statistical experimental design package for use on a personal computer. The total level of phosphite + hindered phenol, and the ratio of phosphite to hindered phenol are used as experimental variables. The approach was tested on extrusions of polypropylene using melt flow retention and yellowness index as observed variables. A quadratic model gave a satisfactory fit to the data for both variables. Contour plots are presented of the performance of the systems for two commercially available hindered phenols and two polypropylene samples. The largest difference between the resins is in the degree of color generation on extrusion. For both hindered phenols, a resin made using “3rd generation” or “high activity” catalyst gave lowest color development on extrusion. There were also small differences in the response of the melt flow of the resins to phosphite level.
    Additional Material: 9 Ill.
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  • 22
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    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 32 (1992), S. 481-487 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The consumption of hot-fillable poly(ethylene terephthalate) bottles is extremely large and is still increasing in Japan. This type of bottle is generally manufactured by the heat-set method using hot molds after stretch-blow molding. In this study, the method is simulated using a setting application in which sheets can be stretched constraining their sizes on a hot aluminum block. The crystallinities of the sheets are found to depend on the thermal history, i.e., the duration and temperature of the heat-set cycle. Heat-setting mitigates thermal-shrinkage of the sheets which is due to the increase in crystallinity or in the tense segments in the amorphous region. The structure of the heat-set sheet varies depending on the original stretched sheet. For a sample of low draw ratio, the crystallinity does not increase because of the heat-set. For a sample of medium draw ratio, the crystallinity increases greatly and the tense segments in the amorphous region also increase because of heat-set. For a sample of high draw ratio, the crystallinity increases a little but the numbers of the crystallite and tense segments in the amorphous region do not change with the heat-set.
    Additional Material: 11 Ill.
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  • 23
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The dynamic behavior of the solution polymerization of styrene in a continuous stirred tank reactor is analyzed with a mixture of tert-butyl perbenzoate and benzoyl peroxide as an initiator system. In the modeling of the reactor, a viscosity dependent reactor wall heat transfer coefficient is used to account for the changing heat transfer efficiency as monomer conversion and polymer molecular weight increase. The steady state and bifurcation behaviors have been investigated with the reactor residence time, initiator feed composition, initiator concentration, feed solvent volume fraction, and coolant temperature as bifurcation parameters. Unlike the reactors with constant heat transfer coefficient, the present system exhibits relatively simple steady state and dynamic bifurcation behaviors. Oscillatory behavior is observed only when the solvent volume fraction in the feed exceeds 0.2. The dynamic simulation of the reactor also indicates that a feedback temperature controller may fail to maintain the reactor temperature when the heat transfer coefficient changes as a result of process disturbances.
    Additional Material: 13 Ill.
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  • 24
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    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 32 (1992), S. 586-592 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Thin microtomed samples from hot-tool butt welds of polypropylene pipes are subjected to uniaxial tensile stress using a specially built instrumented microtesting machine. The deformation of the interface between the weld and the bulk polymer is measured by an optical method. An analysis of these measurements is carried out using the finite element method, and contours of the effective stress are obtained. There is a steep stress gradient at the junction of the weld flash and the bulk polymer, although the stress concentration factor is relatively low. The stress is essentially constant in the bulk polymer apart from the region near the weld zone. Tests on samples without the weld flash show that the maximum stress occurs within the weld zone. This is consistent with long-term tests on larger samples, where the fracture is found to initiate within the weld. The method of analysis enables the stress-strain response of the weld material to be determined.
    Additional Material: 13 Ill.
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  • 25
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 32 (1992), S. 600-611 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Ultrasonic welding of oriented polypropylene (OPP) using tie-layer materials has been examined. The thermal cycle at the joint interface was evaluated using a high speed data acquisition system, and concurrent changes in horn displacement (penetration) and the output power were monitored. The model explaining process operation involves four phases, i.e., I-where heating occurs because of the stresses generated in asperities on the contacting surfaces; II-where the whole tie-layer reaches the melting point; III-where the polymer melt is subjected to intense heating from viscous dissipation and is squeezed out; and IV-where the joint cools after welding. In the early stages of ultrasonic welding the heat generated at asperities on the contacting surfaces leads to melting of the tie-layer/oriented polypropylene interface within 50 ms. The tie-layer heats up because of a combination of viscoelastic dissipation and heat conduction from the oriented polypropylene/tie-layer interface, and the rate of temperature rise at the midline of the tie-layer is in the range 200°/s to 400°/s. The reduction in thickness of the test specimens (penetration) is negligible up to the time when the tie-layer melts completely, and then changes rapidly when the melted polymer at the joint interface is squeezed out. The influence of machine parameters (amplitude and contact pressure) and of tie-layer Melt Flow Index is also examined. The total time required for completion of the welding process decreases when the amplitude and applied pressure are increased. The use of low Melt Flow Index tie-layers produces peak temperature as high as 600° at the bondline, and little material is ejected during the ultrasonic welding operation.
    Additional Material: 19 Ill.
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  • 26
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 32 (1992), S. 810-822 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: This work presents an analytical technique to describe the orientation behavior of short fibers in arbitrary two-dimensional homogeneous flows. It is shown that the fiber orientation, specified by a unit vector, can be analytically calculated at any instant using any initial orientation and flow kinematics. The rotation of a fiber with the bulk fluid deformation is expressed in terms of orientation vector components by utilizing an equivalent strain tensor calculated from the fluid kinematics. This technique is then used to evaluate the orientation behavior of a large number of fibers starting from different initial orientations, representing an orientation state. The orientation distribution function is generated statistically by considering the frequency distribution curve of the orientation of the large number of fibers. It is shown that using a combination of analytical solutions and statistical methods provides a convenient description of fiber orientation behavior. The accuracy of the generated orientation distribution function is found to be dependent on the number of fibers used in the analytical solution. The statistical orientation distribution function is compared with the exact solutions for certain homogeneous flows and found to be in close agreement.
    Additional Material: 16 Ill.
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  • 27
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 32 (1992), S. 836-840 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A commercial epoxy resin, consisting of a mixture of diepoxides based on diglycidyl ether of bisphenol-A (DGEBA) and containing an epoxidized polypropylene glycol as reactive diluent, was characterized by 1HNMR, FTIR, SEC, and chemical analysis. The kinetics of the cure with ethylenediamine (EDA) was catalyzed by the (OH) groups present in a large amount in the commercial formulation. A second order kinetic behavior gave an accurate fitting of results obtained by different experimental techniques (DSC in dynamic and isothermal modes and SEC in the pregel stage). The activation energy was E = 59.1 kJ/mol (14.1 kcal/mol), in very close agreement with values reported for the catalytic mechanism of the DGEBA-EDA polymerization. From the gel conversion and the critical stoichiometric ratio for samples containing an epoxy excess it was found that the average functionality of epoxidized species was f = 1.58.
    Additional Material: 9 Ill.
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  • 28
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 32 (1992), S. 841-844 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Elastic moduli of injection molded blends of polycarbonate with poly(styrene-co-acrylonitrile) (SAN) have been obtained at temperatures between the glass transition temperatures of the two components. When compared with compression molded blends as a function of composition, the moduli were found to differ by as much as a factor of three at intermediate compositions. The variations are ascribed to differences in connectivity between minor component particles. The morphologies of these materials have been modeled using percolation concepts to quantify continuity of the individual phases. The effects of phase continuity resulting from composition as well as dispersed phase shape differences were evaluated. It was found that shape per se has only a minor effect on percolation. However, shape as reflected in the size of dispersed particles relative to the extent of the domain in which they reside is primary for developing a model for continuity of the phases. An empirical relation for percolation in finite domains was devised from Monte Carlo simulations. Modulus values calculated from these continuity considerations agree well with the observed data.
    Additional Material: 5 Ill.
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  • 29
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 32 (1992), S. 854-860 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The morphology, rheology, and mechanical properties of blends of polysulfone (PSF) with up to 65% of a wholly aromatic liquid crystalline polymer (LCP) were investigated. In injection molded specimens a skin-core morphology was observed with the LCP minor phase oriented in the skin and globular in the core. Scanning electron microscopy of fractured surfaces showed sharp phase boundaries, suggesting low interfacial adhesion. The neat PSF and blends with low amounts of LCP exhibited a low shear Newtonian plateau not observed in the blends with high LCP levels. The addition of LCP to PSF resulted in an increase in stiffness, a small increase in tensile strength, and a significant improvement in processability.
    Additional Material: 8 Ill.
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  • 30
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 32 (1992), S. 861-867 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Commercial polysulfone/polycarbonate (PSU/PC) polymer blends were reprocessed up to five times to determine the influence that reprocessing has on their structure and physical properties. All the high strain properties, mainly ductility, significantly decreased under harsh processing conditions, such as five cycles at 320°C. The results of reprocessing the blends at 320°C have been compared with results at a lower temperature and also with those of the separate components with the aim of clarifying the origin of the degradation. These results plus Fourier transform infrared spectroscopy (FTIR), dynamic mechanical analysis, and melt flow index measurements (MFI) indicate that the presence of the two polymers together clearly decreases the resistance to degradation of each component. Moreover, degradation under the stated conditions is mainly thermal and does not change the chemical nature of the blends. However, a clear decrease in molecular weight was observed both by viscosimetry and MFI measurements as was a shift to higher temperatures of the low temperature secondary transition of both PC and PSU. Both molecular weight and secondary transition changes usually deteriorate mechanical properties but not in the degree observed here. This probably means that the fine and difficult-to-observe structure of the blend has also changed.
    Additional Material: 8 Ill.
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  • 31
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 32 (1992), S. 886-893 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Dynamic mechanical thermal analysis (DMTA), differential scanning calorimetry (DSC), and scanning electron microscopy (SEM) concurrently show that polycarbonate (PC)/poly(methyl methacrylate) (PMMA) blends have a two-phase structure. The differences between the Tgs of parent polymers and the Tgs of conjugate phases, determined by both DMTA and DSC, indicate a limited miscibility of components and allow the approximate composition of conjugate phases to be calculated. The Flory-Huggins interaction parameter calculated by using these data assumes values about 0.035 ± 0.010. Phase inversion occurs in an interval close to the 50/50 composition, though the molar masses and melt viscosities of the polymers were rather different. Partial miscibility of components ensures interfacial adhesion capable of sustaining the stress transfer between phases up to fracture. Yield stress of the blends is very close to values foreseen by the rule of mixtures. A specific feature of the blends studied is that the addition of 10 to 20 vol% of PMMA to PC increases the strain at break and work to fracture, which are rather low for the PC used. The enhanced capability of the blends to absorb mechanical energy is probably linked to plastic deformation of the dispersed PMMA.
    Additional Material: 6 Ill.
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  • 32
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    Polymer Engineering and Science 32 (1992), S. 894-902 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: In this work, blends of polycarbonate and a high density polyethylene were investigated through their morphology, mechanical properties, and the effect of compatibilizers: a copolymer styrene-butadiene-styrene and an ionomer. Blending was performed in the melt state at 220°C, and the concentration of the compatibilizers was varied from 1% to 5% by weight. In the case of the copolymer modified blend, the results showed no change in the mechanical properties compared to the neat blend, whereas the morphology showed that the copolymer might interact with only one phase. For the ionomer, the addition of 1% increased the Young's modulus and the tensile strength of the blend. For the morphology, a large change in the size of the dispersed phase (polyethylene) is observed. This was attributed to the compatibility of the ethylene group of the ionomer with the minor phase, and the reaction between the carbonate group of polycarbonate (PC) and the acid group of the ionomer. An investigation on the binary blends of PC and the ionomer showed the occurrence of a chemical reaction that might be of a transesterification type. Differential scanning calorimetry and Fourier transform infrared techniques were used to characterize these blends.
    Additional Material: 18 Ill.
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  • 33
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 32 (1992) 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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  • 34
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 32 (1992), S. 921-923 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The melt flow index and oxidation induction period of low-density polyethylene crosslinked with dicumyl peroxide (DCP) in the presence of tetrakis (methylene β-3, 5-di-butyl-4-hydroxypheny1)-propionate methane (Antioxidant 1010) were determined. The results suggest that there is a negative synergism between this crosslinking agent and antioxindant. Part of the antioxidant terminated the chain propagation by trapping radicals, and thus reduced the efficiency of crosslinking. The antioxidant efficiency was also reduced owing to meaningless consumption.
    Additional Material: 4 Ill.
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  • 35
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    Polymer Engineering and Science 32 (1992), S. 909-919 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Fractography has been used in the post-failure analysis of single edge notched specimens of injection molded blends of polycarbonate (PC) and acrylonitrile-butadiene-styrene terpolymer (ABS). The mode of ductile tensile fracture of single edge notched specimens depended on comosition. Plane stress shear tearing was observed in the composition range PC/ABS 90/10 to 70/30 by weight where PC was the continuous phase. Intermediate compositions, PC/ABS 60/40 to 40/60, had a co-continuous or almot co-continuous phase morphology; these blends fractured by mixed mode pop-in, where a tunneling center crack relieved the triaxiality and permitted plane stress shear lips to form near the edges. Herringbone fracture, a plane strain mode characterized by discontinuous crack growth, was observed when ABS was the continuous phase, PC/ABS 30/70 to 10/90. An S-shaped relationship was observed between the ductile-to-brittle transition temperature and the composition. Addition of ABS to PC increased ductility up to PC/ABS 70/30 and 60/40, which were the most ductile compositions. Further addition of ABS decreased the ductility, and the least ductile compositions were PC/ABS 30/70 and 10/90.
    Additional Material: 12 Ill.
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  • 36
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    Polymer Engineering and Science 32 (1992), S. 1086-1096 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A finite element algorithm developed previously has been successfully extended to the study of nonlinear time-dependent problems. Nonlinear viscoelastic and viscoplastic models have been used to study the time-dependent deformation and failure of high density polyethylene (HDPE). Two classes of nonlinear models have been identified; those that allow stress redistribution with time under specified traction boundary conditions, and those that do not. The implications of using viscoelastic vs. viscoplastic models, as well as the specific mathematical form of the constitutive equations selected for use, have been studied. Strains predicted using the FE algorithm have been compared with experimental measurements for (i) a HDPE plate with a hole and (ii) a double edge notch HDPE specimen, both under remote tension. Excellent agreement was obtained between numerical predictions and the experimental values.
    Additional Material: 15 Ill.
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  • 37
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    Polymer Engineering and Science 32 (1992), S. 1105-1113 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The influence of sample thickness on fatigue crack propagation rates in injection molded nylon 66 was determined by preparing 12.7 mm thick plaques along with more conventional 3.0 mm thick samples. Initial results suggested a large effect of thickness as the crack propagation rates were accelerated in the thicker samples and the stress dependence was also increased. Since the calculated thickness for a plane stress to plane strain transition in nylon 66 is 9.0 mm, it was thought that these results were related to the stress state at the crack tip. However, a more thorough study of the thicker plaques has now demonstrated that neither the magnitude nor the stress dependence of the fatigue crack growth rates is necessarily changed under plane strain conditions as similar results can be obtained for thick and thin plaques. It is suggested that the earlier results were confounded by a previously unrecognized processing history effect which does accelerate fatigue fracture. The latter effect is shown by thermal analysis and optical microscopy to be related to a rearrangement of the polymer network during melt processing.
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  • 38
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    Polymer Engineering and Science 32 (1992), S. 1114-1125 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Fatigue crack propagation rates in injection molded nylon 66 were previously shown to be strongly affected by prior processing history. To provide a physical basis for the observed acceleration in crack growth rates, microtomed sections were cut through the tips of stable fatigue cracks and examined by optical microscopy. A reduction in spherulite size occurs with reprocessing along with an accompanying decrease in the amount of deformation at the crack tip. For the initially processed nylon 66 this deformation consists of a vast array of independently initiated craze-like zones. Patchy type regions observed on the fatigue fracture surface are similar in size to the initially formed crazed zones. Crack advance occurs by the breakdown and coalescence of the crazed regions via matrix shearing. The extensive damage zone is believed to result in a reduction in stress intensity at the crack tip thereby reducing the crack propagation rates. For the reprocessed nylon 66, one observes fewer crazes and a sharper fatigue crack tip with a consequent acceleration in crack propagation rates and a smoother fracture surface.
    Additional Material: 19 Ill.
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  • 39
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    Polymer Engineering and Science 32 (1992), S. 1126-1137 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Brittle failure, a significant design issue for plastic components subject to impact loads, is especially catastrophic when the material is normally ductile. Such behavior is not adequately understood relative to the micromechanisms, controlling parameters, and design consequences in plastics. Previous work has identified the process of crazing as being relevant to these failures in thermoplastics. The relationship between crazes generated through mechanical loading and subsequent brittle failure of amorphous thermoplastics is discussed and the hypothesis that the craze event is a necessary but insufficient condition for brittle failure is employed. Emphasis is focused upon the engineering prediction of craze formation and its use as a conservative brittle failure criteria for defining geometric details to prevent brittle failure. First, a series of experiments using one geometry is applied to study the concept of crazing as a precursor to brittle fracture in the two amorphous polymers polycarbonate and polyetherimide. Second, three-dimensional finite element analyses are used to assess the effects of changes in geometric detail upon the continuum stress state and eventual failure of the specimen for these two materials.
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  • 40
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    Polymer Engineering and Science 32 (1992), S. 1138-1146 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The compressive-stress strain response of polyurethane foam under uniaxial compressive impact loading has been studied. The development of a uniaxial constitutive model from strain rate controlled compression tests is detailed. Density and temperature functions have been added to the integral power model proposed by Schwaber, Meincke, and Nagy. The model assumes that the effects of density, temperature, strain and strain rate on stress are separable functions. The model correlated well with actual static compression tests and was used successfully to predict the impact response of energy absorbing polyurethane foam under uniaxial compressive loading.
    Additional Material: 15 Ill.
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  • 41
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 32 (1992) 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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  • 42
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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  • 43
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    Polymer Engineering and Science 32 (1992), S. 1163-1173 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: This paper exmines the influence of process variables on final thickness distributions for vacuum-formed thermoplastic parts. The process variables investigated include evacuation rate, sheet surface temperature, mold temperature, and material slip over the mold surface. The experimental data presented include, in addition to thicknesses, sheet surface temperature obtained via infrared thermography. A finite element program to model the vacuum-forming process is discussed, and the wall thickness distribution predicted by this program for a vacuum-formed part is compared with the results of the experiments.
    Additional Material: 16 Ill.
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  • 44
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    Polymer Engineering and Science 32 (1992), S. 1350-1357 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The dynamic creep behavior of a filled poly(dimethylsiloxane) elastomer was studied under cyclic stress. The stress level was chosen such that the increase in the internal temperature was small and that microcracks were not observed. This work has demonstrated that cyclic stress in combination with high temperature accelerates the degradation of the elastomer. The results suggest that because of the applied force, breaks in the load-bearing chains of the network occur. These breaks, while relieving the mechanical stress, create highly reactive ionic fragments. It is believed that because of the subsequent reactions of the ionic fragments, changes in the specific gravity, storage modulus, effective crosslink density, and length of the sample (creep) are observed. The observed decrease in the storage modulus is thought to occur because of the reaction of the ionic fragments with moisture, which results in the formation of silanol chain ends that reduce the effective crosslink density. The results also show that contrary to the prediction of the Boltzmann's Superposition Principle, the rate of creep is greatly enhanced when the sample is subjected to a sinusoidally varying dynamic load as compared to a comparable static load. The polymer weight loss was found to be linear with time and strongly dependent on the level of applied dynamic and static force. In addition, the weight loss and rate of creep were also found to be strongly dependent upon temperature.
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  • 45
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    Polymer Engineering and Science 32 (1992), S. 1358-1365 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Interest in the development of polymeric materials for high temperature, electronic and microelectronic applications has led to an increasing number of new polymers. Many of these polymers have complex organic ring structures and semirigid backbones, characteristics that have posed some difficulties for structural analysis. The purpose of this paper is to test and compare two practical nondestructive optical techniques, polarized optical microscopy and polarized refractometry, for the determination of three-dimensional surface and bulk anisotropy in these advanced materials. The optical techniques are first tested on a series of optically homogeneous uniaxially oriented isotactic polypropylene films and then applied to the analysis of high refractive index Kapton (PMDA-ODA) polyimide films. The study includes a test of the validity of the compensator method, including the effect of fringe jumping, the use of polymer retarders, and the tilting technique of Stein.
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  • 46
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    Polymer Engineering and Science 32 (1992), S. 1372-1378 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Polymer coatings are widely used to protect glass from indentation damage. A model for the strength degradation that occurs when a sharp indenter penetrates through the coating is developed by accounting for the indentation load shared by the coating and substrate. This model accounts for the additional load supported by the coating due to the pile-up of coating material underneath the indenter. The model predicts the strength degradation as a function of indentation load, coating and substrate hardnesses, and coating thickness. Comparison of the model to experimental data for a wide range of polymer coatings (two epoxies, epoxy acrylate, and urethane acrylate) on soda-lime glass substrates shows good agreement.
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  • 47
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    Polymer Engineering and Science 32 (1992), S. 1500-1508 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Novolak resins provide the best overall performance for “g” and “i”-line photoresists. There is a continuing need for advanced novolak designs that will provide improved lithographic, thermal, and etch characteristics that may be reproducibly synthesized. A novolak synthesis process was developed using the solution condensation technique. Cresol mixtures with m-cresol and 3,5-xylenol at specific ratios provide reproducible novolaks with controlled molecular weights. In order to achieve high thermal and etch performance, while retaining photospeed and resolution characteristics, three basic approaches were investigated: (1) increase in molecular weight, which produces novolaks with Tg ranging from 120 to 130°C with relatively slow dissolution rates; (2) incorporation of multi-hydroxyphenols such as resorcinol to tailor the dissolution rate, resolution, thermal, etch, and adhesion characteristics; (3) partial esterification of multi-hydroxy novolaks giving a Tg range of 140 to 150°C. Lithographic evaluation of the novolak resins was performed by formulating with a 2,1,4-diazonaphthoquinone (DNQ) sensitizer. Results on resin synthesis, molecular weights, lithographic, thermal, and etch characteristics are discussed.
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  • 48
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    Polymer Engineering and Science 32 (1992), S. 1511-1515 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The quantum yield for acid generation from alkyl and arylsulfonic acid esters of pyrogallol was measured in resist films composed of a sulfonate, tBOC-BA, and novolak resin. It was found that the quantum yield increases with decreasing molecular size of the sulfonyl group, which can explain the differences in sensitivity of the resist systems. Methanesulfonic acid esters of various phenol derivatives were synthesized to see the effect of backbone structure on the efficiency of acid generation. The sensitivity measurement of resists containing these sulfonates indicates that the number of sulfonyloxy groups bonded to a benzene ring is important. The higher number of the sulfonyloxy groups gives a higher efficiency of acid generation.
    Additional Material: 6 Ill.
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  • 49
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 32 (1992), S. 1516-1522 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: t-Butyloxycarbonyl (t-BOC) blocked compounds based on the protection of phenolic groups, e.g. poly-4-hydroxystyrene derivatives, Bisphenol A type dissolution inhibitors, or onium salt photoacid generators, have found widespread research interest for photoresist systems with excellent photosensitivity and high resolution power. We have made an extension of this approach using new phenol type polymers. This contribution presents first details on the chemistry of these systems and results of their lithographic evaluation as positive tone photoresists for deep UV applications.
    Additional Material: 11 Ill.
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  • 50
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 32 (1992) 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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  • 51
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 32 (1992), S. 1557-1557 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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  • 52
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 32 (1992), S. 1545-1549 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The multiple interference effect is one of the major causes of the fluctuation in critical dimension control (CD) and in mark detection for alignment. Suppressing this effect is critical for future photolithography. We propose a new photolithography technique called anti reflective coating on resist (ARCOR), which improves linewidth accuracy and overlay accuracy by suppressing multiple interference. ARCOR consists of relatively simple processes: A clear antireflective film is spun onto the resist prior to the mark detecting for alignment and exposure. The film is subsequently removed and the resist developed in the conventional way. ARCOR differs from ARC, which suppresses the reflection at the resist/substrate interface. ARCOR suppresses the reflection at the air/resist interface. ARCOR allows mark detection and exposure without light intensity-loss and multiple interference. The experiments mainly examine polysiloxane and perfluoroalkylpolyether as ARCOR materials. It is shown that linewidth accuracy can be improved from 0.3 to 0.03 μm. The signal-to-noise ratio of the alignment signal is drastically improved, and the overlay error is about half that of the conventional method. ARCOR is also effective for directly measuring the reflectivity at the resist/substrate interface, which is a key parameter of the multiple interference effect and the halation. Using ARCOR and a thin resist film, the measured ratio of reflected light to incident light indicates the reflectivity at the resist/substrate interface. Because, the probe light does not reflect off the resist surface and the intensity-loss at the resist surface is suppressed. With perfluoroalkylpolyether film, the measurement error is ∼ 1.5%.
    Additional Material: 9 Ill.
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  • 53
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 38 (1992), S. 15-25 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Quantitative results are presented on mean coordination number and coordination number distribution, contact normal distribution and fabric tensor of simulated anisotropic granular deposits with resulting solid fractions between ca. 15% for ballistic deposits and 58%, corresponding to a random loose packing. The deposits, generated by the capture of uniform size spherical particles arriving normal to a target, were simulated using a simple algorithmic model.We focus on microstructural quantities which explicitly take into account the discrete nature of the granules comprising the deposit. Such measures are important in determining the heat transport properties of the deposits for Fourier conduction through the solid phase, as well as their mechanical and sintering properties. The variation of mean coordination number with deposit solid fraction was successfully correlated using a unit-cell model (Eq. 13). This correlation, in conjunction with entropy maximization arguments (after Nayak and Tien, 1978) has been further used to predict the coordination number distribution. The usefulness of the results reported here is illustrated by computing an upper bound to the deposit effective thermal conductivity (Jagota and Hui, 1990) and comparing it to both ‘exact’ simulation results (Tassopoulos and Rosner, 1991b) and experimental data (Koh, 1971).
    Additional Material: 9 Ill.
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  • 54
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 38 (1992), S. 56-66 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The tortuosities of fibrous media in the heretofore unexplored transition and ordinary regimes are computed using a Monte Carlo scheme based on the Einstein equation for random walkers. The model structure is that of fully penetrable cylinders (FPC) in a unit simulation volume. The mean square displacement technique is combined with the first passage time distribution to accelerate the progress of the walkers at low Knudsen number. The results include the computation of transition regime transport coefficients for the first time. The calculated ordinary tortuosities are approximately equal to the reciprocal of the porosity over a wide range, while the transition tortuosities are shown to deviate from the reciprocal porosity with a simple dependence on Knudsen number. The limits of the transition regime are shown to correspond roughly to Knudsen numbers of 0.50 and 100, respectively. The calculated Knudsen tortuosities are shown to improve on earlier results obtained by the authors using a flux-based technique.
    Additional Material: 10 Ill.
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  • 55
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 38 (1992), S. 101-115 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Singularity theory, large activation energy asymptotics, and numerical methods are used to present a comprehensive study of the steady-state multiplicity features of three classical adiabatic autothermal reactor models: tubular reactor with internal heat exchange, tubular reactor with external heat exchange, and the CSTR with external heat exchange. Specifically, we derive the exact uniqueness-multiplicity boundary, determine typical cross-sections of the bifurcation set, and classify the different types of bifurcation diagrams of conversion vs. residence time. Asymptotic (limiting) models are used to determine analytical expressions for the uniqueness boundary and the ignition and extinction points. The analytical results are used to present simple, explicit and accurate expressions defining the boundary of the region of autothermal operation in the physical parameter space.
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  • 56
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 38 (1992), S. 153-157 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 5 Ill.
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  • 57
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    AIChE Journal 38 (1992), S. 318-319 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 10 Ill.
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  • 58
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    AIChE Journal 38 (1992), S. 321-327 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Aqueous solutions of phenol were oxidized in a flow reactor at temperatures between 300 and 420°C (0.89 ≤ Tr ≤ 1.07) and pressures from 188 to 278 atm (0.86 ≤ Pr ≤ 1.27). These conditions included oxidations in both near-critical and supercritical water. Reactor residence times ranged from 1.2 to 111 s. The initial phenol concentrations were between 50 and 330 ppm by mass, and the initial oxygen concentrations ranged from 0 to 1,100% excess. The oxidation experiments covered essentially the entire range of phenol conversions. Analysis of the kinetics data for phenol disappearance using a combination of the integral method and the method of excess revealed that the reaction was first order in phenol and 1/2 order in oxygen, and influenced by pressure. The global reaction order for water was taken to be nonzero, and the global rate constant was assumed to be independent of pressure so that the only effect of pressure was to alter the water concentration and hence the reaction rate. This approach led to a global reaction rate law that was 0.7 order in water and had a rate constant with an activation energy of 12.4 kcal/mol. The implications of these rate laws to the design of a commercial supercritical water oxidation reactor are also explored.
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  • 59
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    AIChE Journal 38 (1992), S. 1027-1037 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A mathematical model is presented to describe coking and activity characteristics of porous catalysts in supercritical reaction mixtures. These characteristics are determined by the way in which temperature and pressure affect the simultaneous physicochemical rate processes involving the effective diffusion of reactants in the pore, coke formation, and coke extraction. For a parallel coking reaction, the model predicts that when the reaction mixture density is isothermally increased from subcritical to low-to-moderate values, the ensuing higher reaction rates and restricted diffusion lead to pore-mouth plugging and decreased catalyst effectiveness factors. At dense supercritical conditions, however, the enhanced coke solubilities in the reaction mixture alleviate pore-mouth restrictions, resulting in a recovery of catalyst activity and increased effectiveness factors. The model predicts an optimum supercritical density at which catalyst activity is maintained at a maximum value. At smaller than optimum density values, the reaction rate is limited by coke extraction and at larger than optimum values, the rate is subject to pore diffusion limitations. These predictions are qualitatively consistent with reported experimental observations.
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  • 60
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    AIChE Journal 38 (1992), S. 1079-1091 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A computer model for a hot gas-fluidized bed has been developed. The theoretical description is based on a two-fluid model (TFM) approach in which both phases are considered to be continuous and fully interpenetrating. Local wall-to-bed heat-transfer coefficients have been calculated by the simultaneous solution of the TFM conservation of mass, momentum and thermal energy equations. Preliminary calculations suggest that the experimentally observed large wall-to-bed heat-transfer coefficients, frequently reported in literature, can be computed from the present hydrodynamic model with no turbulence. This implies that there is no need to explain these high transfer rates by additional heat transport mechanisms (by turbulence).The calculations clearly show the enhancement of the wall-to-bed heat-transfer process due to the bubble-induced bed-material refreshment along the heated wall. By providing detailed information on the local behavior of the wall-to-bed heat-transfer coefficients, the model distinguishes itself advantageously from previous theoretical models. Due to the vigorous solids circulation in the bubble wake, the local wall-to-bed heat-transfer coefficient is relatively large in the wake of the bubbles rising along a heated wall.
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  • 61
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    AIChE Journal 38 (1992), S. 1129-1134 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 4 Ill.
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  • 62
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 38 (1992) 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 63
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 38 (1992), S. 1-14 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Adaptive control techniques, with their capability for providing satisfactory control even when the process changes with time, are promising candidates for dealing with common problems encountered in photolithography processing such as batch-to-batch variations in resist properties and inconsistencies in resist curing. In this article, an adaptive control strategy for the photolithography process is proposed and evaluated. The design utilizes a reduced-order lithography model, an on-line parameter estimator, and a nonlinear model-inversion controller.The width of the printed resist lines, a crucial output of photolithography, is controlled by automatically adjusting the exposure energy. In the calculation of the appropriate exposure adjustment, the controller uses both measured critical-dimensions as well as estimated values produced by the process model. The control system is capable of tracking changes in the photolithography process by automatic updating of key model parameters as the process evolves in time. Simulation studies of the closed-loop adaptive control strategy, using the PROLITH simulation package to represent the lithography process, demonstrate the feasibility of this approach.
    Additional Material: 16 Ill.
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  • 64
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    AIChE Journal 38 (1992), S. 76-82 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The liquid circulation model of Rice and Geary (1990) is extended to include turbulence originating at the wall. Thus, two possible length scales are considered: one originating from rising bubbles and the other emanating from the wall. The appropriate scale for small columns should be based on bubble size, while for larger systems the proper mixing length is proportional to column diameter. It is proposed that the film Reynolds number may be the key in distinguishing the two cases.
    Additional Material: 4 Ill.
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  • 65
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    AIChE Journal 38 (1992), S. 116-127 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Singularity theory is combined with asymptotic analysis to determine the exact uniqueness-multiplicity boundary and ignition and extinction locus for the non-adiabatic, autothermal tubular reactor model. It is found that the steady-state behavior of the nonadiabatic reactor is described by the two limiting cases of adiabatic and strongly cooled models. The adiabatic case has been examined in a previous study. Here, we develop limiting models to describe the strongly cooled asymptotes. We also classify the different types of bifurcation diagrams of conversion vs. residence time using the results of singularity theory with a distinguished parameter. Analytical criteria are developed for predicting the conditions under which autothermal operation is feasible when heat losses are significant.
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  • 66
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    AIChE Journal 38 (1992), S. 149-152 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 4 Ill.
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  • 67
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 38 (1992) 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 68
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    AIChE Journal 38 (1992), S. 201-210 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Two-and one-dimensional steady-state isothermal mathematical models of monolith reactors for selective catalytic reduction (SCR) of NOx by NH3 are compared for circular, square and triangular geometry, as well as for linear and Rideal kinetics. Solutions for the two-dimensional model demonstrate that, as the reaction rate decreases from infinity to zero, the Sherwood number varies from the values of the Nusselt number characteristic of the Graetz-Nusselt problem with constant wall temperature to those with constant wall heat flux but with peripherally varying temperature. A lumped-parameter treatment, based on similarity with the constant wall temperature heat transfer problem, agrees satisfactorily with the solutions for a far more expensive two-dimensional model. The agreement is excellent for square channels, but the NH3 slip tends to be underestimated in the triangular geometry. The one-dimensional model reproduces successfully experimental effects of the NH3/NO feed ratio, and of the area velocity and the size of monolith channels.
    Additional Material: 8 Ill.
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  • 69
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    AIChE Journal 38 (1992), S. 219-226 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Current AC (alternating current) techniques are used often to characterize the energetics at a semiconducting solid phase/electrolyte interface. For thin layers having a strongly disordered or amorphous structure (such as oxide-passive layers anodically grown on valve metals), interpretative models currently used for crystalline semiconductors may produce misleading data.A new interpretation of the admittance data, based on recent models for amorphous semiconductors (a-Sc) Schottky barriers, is presented for passive films of Nb, W and Ti. The physical bases of the model are presented as well as its advantages and disadvantages. The new theory views the solid/electrolyte interface more satisfactorily and provides information on the solid-state properties and the electronic structure of the electrode useful for interpreting the electron exchange between the solid phase and redox couples in solution.
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  • 70
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    AIChE Journal 38 (1992), S. 26-40 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The design of controllers for nonlinear, nonminimum-phase processes is one of the most difficult control problems currently faced. Current available control algorithms for nonlinear processes rely implicitly or explicitly on an inverse of the process. Linear control methods for nonminimum-phase processes are based on a decomposition of the process into a minimum-phase and a nonminimum-phase part. Such a decomposition is an open problem for nonlinear systems.In this work, a control structure called the minimum-phase output predictor for nonlinear, nonminimum-phase processes is developed. The structure is based on the notion of statically equivalent outputs; a minimum-phase, statically equivalent output is estimated on-line and then an available nonlinear control algorithm is used to control it to set point. The advantage of the proposed formulation is that it is based on the calculation of an output function, not on a decomposition of the process dynamics. The proposed control methodology is applied and its performance is evaluated for a chemical engineering example.
    Additional Material: 8 Ill.
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  • 71
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    AIChE Journal 38 (1992), S. 67-75 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Clarke et al. (1986) have developed a model-based verification method and have applied it to validation of VLSI circuits. We have used the method to test automatically the safety and operability of discrete chemical process control systems. The technique involves: (1) a “system model” describing the process and its software; (2) “assertions” in temporal logic expressing user-supplied questions about the system behavior with respect to safety and operability; and (3) a “model checker” that determines if the system model satisfies each of the assertions and provides a counterexample to locate the error if one exists. Temporal logic is used for reasoning about occurrence of events over time. To reveal discrete event errors, we have applied the verification method to a simple combustion system and an alarm acknowledge system.
    Additional Material: 18 Ill.
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  • 72
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    AIChE Journal 38 (1992), S. 93-100 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: One of the major obstacles to overcome for the realization of economical hydrogen-oxygen, polymer-electrolyte fuel cells is the high capital cost of the inert perfluorosulfonic acid (PSA) membranes, which provide a pathway for ionic transport between the cell electrodes. It has recently been shown that composite polymer membranes can be synthesized by depositing PSA polymers onto porous poly(tetrafluoroethyene) (PTFE) substrates. The resulting membranes are mechanically durable and quite thin relative to traditional PSA membranes; we expect the composite membranes to be of low resistance and cost. In this experimental study, we examine the composite membrane properties as a function of the membrane composition. Our results allow us to form a conceptual model to explain both the equilibrium and transport characteristics of these materials. For high PSA contents, the membrane behavior is similar to that of the PSA polymer; the water permeability, however, is reduced significantly. For intermediate PSA contents, the membranes have a high porosity and match the thickness of the PTFE substrate (≈50 μm); membranes of this composition range are potentially useful candidates for fuel cells because of their high resistance to water transport and reduced ionic resistance. Composite membranes of very low PSA content demonstrate characteristics similar to the hydrophobic PTFE substrate and are not of interest for fuel cells.
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  • 73
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    AIChE Journal 38 (1992), S. 479-479 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 74
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    AIChE Journal 38 (1992), S. 489-501 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The coupled, unsteady Navier-Stokes, convective diffusion, and thermal energy equations that describe spin coating of colloidal suspensions are solved numerically. The theoretical model, absent of any adjustable parameters, is used to explore the effects of angular velocity, initial solvent weight fraction, solvent properties and spin coating protocol on the evolution of temperature and concentration profiles in the liquid film during spin coating. The predicted coated film thickness is found to be in excellent quantitative agreement with spin coating experiments performed with both hard-sphere and nonhard-sphere suspensions of monodisperse latex particles in water. The coated film thickness, determined by ellipsometry, is shown to depend on the inverse square root of the angular velocity except at high ionic strength when the dependence on angular velocity is weaker. Timescales that characterize spin coating of colloidal suspensions are shown to be quite different from those that characterize spin coating of polymer solutions, and consequently simple models for predicting the coated film thickness of polymer solutions (Bornside et al., 1991; Lawrence, 1989) are shown to be inadequate for colloidal suspensions. Rapid substrate acceleration, high rotation rates, partial saturation of the overlying gas phase, and high initial solids concentration are identified as spin coating protocols that suppress a convective instability that produces radial striations in the coated film.
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  • 75
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    AIChE Journal 38 (1992), S. 535-543 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A hybrid model is developed and implemented for predicting the limiting bound of the reactant conversion rate in an isotropic turbulent flow under the influence of a reaction of the type A + B Products. This model is based on the amplitude mapping closure of Kraichnan for the molecular mixing of a stochastically distributed scalar, and the eddy-damped quasi-normal Markovian (EDQNM) spectral closure for the two-point scalar covariance. The results predicted by this model compare well with available experimental data in both gaseous and aqueous plug-flow reactors, but point to the need for more detailed measurements in future experimental studies. With the implementation of the mapping closure, a simple analytical expression is obtained for the decay rate of the unmixedness. This expression is very convenient and is recommended for direct practical applications in the modeling and design of plug-flow reactors.
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    AIChE Journal 38 (1992), S. 237-243 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: An experimental study has been carried out of the in situ thermal degradation of a commercial dehydrogenation catalyst in a fixed-bed reactor. The activity of catalyst particles sampled at different reactor positions after several reaction-regeneration cycles has been related to their time-temperature history, according to the following kinetics: \documentclass{article}\pagestyle{empty}\begin{document}$$ - da_0 /dt = 0.147{\rm exp}(- 73,600/RT)a_0^{2.2} $$\end{document}The above equation represents the loss of activity under coke-free conditions, that is, activity loss due to sintering. The results of the study show that important differences in catalytic activity can be obtained for different positions of a fixed-bed catalytic reactor after several operation-regeneration cycles.
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    AIChE Journal 38 (1992), S. 259-272 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The diffusion of proteins in polymer matrices is an important step in the adsorptive and chromatographic processes used for protein purification, as it is often rate-limiting. Methods for the estimation of the intraparticle diffusivity in polymer gels have been developed and were applied to the diffusion of seven model proteins in agarose particles. The intraparticle diffusivity was not affected by particle diameter. A correlation based on the restricted diffusion model of Ogston et al. (1973) and Cukier (1984) has been proposed. This correlation allows the estimation of protein diffusivity in these matrices based on the molecular weight of the protein and the polymer concentration.
    Additional Material: 13 Ill.
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  • 78
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    AIChE Journal 38 (1992), S. 291-296 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The concept of optimal catalyst activity distribution is studied experimentally for the ethylene epoxidation reaction network on a Ag/α-Al2O3 catalyst in a single-pellet reactor. The Dirac delta-type distribution of the catalyst is approximated by a step distribution of narrow width. For a fixed amount of silver, the influence of location and width of the catalytically active layer on the conversion of ethylene and on the selectivity and yield to ethylene oxide is investigated under oxygen-rich conditions in the temperature range 210-270°C. The results clearly demonstrate that for optimum selectivity and yield to ethylene oxide, the silver catalyst should be placed in a thin layer at the external surface of the pellet.
    Additional Material: 6 Ill.
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  • 79
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    AIChE Journal 38 (1992), S. 315-315 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 80
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    AIChE Journal 38 (1992), S. 1871-1880 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The dynamic behaviour of an adiabatic tubular plant reactor during the startup is demonstrated, together with the impact of a feed-pump failure of one of the reactants. A dynamic model of the reactor system is presented, and the system response is calculated as a function of experimentally-determined, time-dependent, manipulated variables. The values of model parameters are estimated by using the SimuSolv (1991) computer program. The data set collected during the reactor start-up is used for the parameter estimation procedure. An excellent agreement is obtained between the experimental and the calculated system response. Many continuously-operated commercial reactors require a complete conversion of one of the main reactants at the reactor exit. It is shown that for an industrial tubular reactor a much higher initial reactor temperature is required during the startup, compared to the reactor inlet temperature during normal steady-state operation, to ensure a complete reactant conversion. Much more research is necessary to determine whether this is a generally valid rule.
    Additional Material: 11 Ill.
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  • 81
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    AIChE Journal 38 (1992), S. 1913-1915 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A semi-empirical model of the radial segregation of solids in upward flow of dilute gas-particle suspensions in riser systems is presented on the basis of a reduced form of the fundamental two-phase flow governing equations and experimental evidence concerning the solids concentration at the wall. The following simple expression for the radial solids concentration profile is obtained: \documentclass{article}\pagestyle{empty}\begin{document}$$ \frac{{1 - {\rm \varepsilon }}}{{{\rm 1} - {\rm \varepsilon }}} = 2\left( {\frac{r}{R}} \right)^2 $$\end{document} and is in agreement with experimental data over a wide range of operating conditions: superficial gas velocity from 1.4 to 15.3 m/s, riser diameter from 0.032 to 0.40 m, imposed solids flux from 6.60 to 207 kg/m2·s, mean particle size from 32 to 120 μm and particle density from 1,000 to 3,500 kg/m3.The model confirms the existence of the core-annulus flow structure in gas-particle suspensions reported in riser reactors, circulating fluidized beds, and the freeboard of bubbling fluidized beds.
    Additional Material: 2 Ill.
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  • 82
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    AIChE Journal 38 (1992), S. 835-846 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Batch, fed-batch, and single-stage CSTR bioreactors operate without external sources of biomass after they have been inoculated. However, other kinds of bioreactors, such as the second and subsequent reactors in a cascade of CSTRs, operate with continuous introduction of biomass from one or more external sources. The biomass in a bioreactor with an external source is not homogeneous with respect to past history of environmental conditions, and growth of this biomass is not balanced (steady-state) growth even when the bioreactor operates in steady state. So-called unstructured models of growth, which assume biomass to lack any internal structure or to have an invariant internal state, can give only a first approximation to the growth rate behavior of the biomass in a bioreactor with an external source of biomass. Structured models, which endow biomass with a changeable internal structure, are required to obtain more accurate predictions of growth rate behavior in such reactors. Introduction of structure is not sufficient for improved accuracy, however, and the fact that biomasses from different sources are remain segregated from one another must also be accounted for by any structured growth model used. This article presents, among others, the systems of different equations that result from application of the notions to the reactors of a cascade of CSTRs.
    Additional Material: 1 Ill.
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  • 83
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    AIChE Journal 38 (1992), S. 1309-1328 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: We examine the simplest homogeneous azeotropic distillation sequence of industrial relevance, where an entrainer is added to a binary azeotrope to recover both azeotropic constituents as pure products. Despite its apparent simplicity, such distillation columns can exhibit an unusual behavior not observed in zeotropic distillation: For some mixtures, separation as a function of reflux goes through a maximum. At infinite reflux, no separation is achieved.In some cases, achieving the same specifications with a larger number of trays requires a larger reflux.Sometimes the only feasible separation yields the intermediate component as a pure distillate, while the bottom product contains the light and heavy components.Sometimes the only feasible separation yields the intermediate component as a pure bottom product while the distillate contains the light and heavy components.While these unusual features can be regarded as curiosities, they are essential for proper entrainer selection and design. For a minimum boiling azeotrope, the existing and conflicting entrainer selection rules state that one should use a component that introduces no distillation boundary between the azeotropic constituents (Doherty and Caldarola, 1985), and either a low or high boiling component that introduces no additional azeotrope or a component which introduces new minimum boiling azeotropes (Stichlmair et al., 1989). By taking advantage of the curious aforementioned features, as well as our experience involving more than 400 mixtures, we have been able to analyze the assumptions behind these criteria, show when those assumptions break down, and therefore understand the limitations of the criteria.
    Additional Material: 61 Ill.
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  • 84
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    AIChE Journal 38 (1992), S. 1161-1169 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The overlapping grain model was used to describe the sulfidation of zinc oxide and zinc-titanium oxide powders at temperatures between 400-700°C in H2S-H2-N2 gas mixtures. Experimental data were collected under conditions free of mass-transfer and pore diffusion limitations. Thus, the only resistances to reaction were due to intrinsic sulfidation kinetics (surface reaction) and diffusion through the product layer. The product layer diffusion coefficient was used as a fitting parameter in the model. As the relative amount of titanium in the sorbent was increased, the product layer diffusion coefficient decreased. Similar activation energies (26.6 kcal/mol) were obtained for the product layer diffusion coefficient of ZnO and Zn-Ti-O sulfidation. From the similarity in activation energies, it is proposed that for both types of sorbents diffusion occurs primarily through ZnS.
    Additional Material: 12 Ill.
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  • 85
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    AIChE Journal 38 (1992), S. 1243-1253 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The degree of hydrogen bonding and macroscopic thermodynamic properties for pure and mixed fluids are predicted with the hydrogen bonding lattice fluid (LFHB) equation of state over a wide range in density encompassing the gas, liquid and supercritical states. The model is successful for molecules forming complex self-associated networks, in this case pure methanol, ethanol, and water, and the mixture 1-hexanol-SF6. In supercritical water, significant hydrogen bonding is still present despite all the thermal energy and is highly pressure- and temperature-dependent. A fundamental description of pressure and temperature effects on hydrogen bonding is presented for a well-defined case, the formation of a complex between a donor and acceptor in an inert solvent, where no self-association is present. The partial molar enthalpy and volume change on complexation both become pronounced near the critical point, where the density is highly variable with temperature and pressure.
    Additional Material: 14 Ill.
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  • 86
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    AIChE Journal 38 (1992), S. 1477-1480 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 5 Ill.
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  • 87
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    AIChE Journal 38 (1992), S. 1488-1488 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 88
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    AIChE Journal 38 (1992), S. 1493-1498 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Racemic leucine can be separated into d- and l-isomers by fractional extraction across microporous hollow fibers. In this extraction, an aqueous solution of the racemate is fed to the lumen of the fibers, and an octanol solution of dodecyl-l-hydroxyproline flows countercurrently outside of the fibers. The interface between feed and extractant is stabilized by filling the pores in the hollow-fiber walls with a cross-linked polyvinylalcohol gel which offers negligible resistance to mass transfer. The extraction with dodecyl-l-hydroxyproline deliberately imitates earlier studies, facilitating comparisons of hollow-fiber extraction with other techniques. The results show that the isomer yield per equipment volume of racemic separation is 100 times greater than that in a continuously rotating extractor, and 1,000 times greater than that in a conventional packed tower.
    Additional Material: 5 Ill.
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  • 89
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    AIChE Journal 38 (1992), S. 1609-1617 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Wrong-way behavior refers to a large transient temperature increase caused by a sudden reduction in the feed temperature or increase in the feed rate to a packed-bed reactor operating at an intermediate or high level of conversion. This dynamic temperature rise may be affected by reactant adsorption on the inert catalyst support. The wrong-way behavior usually leads to formation of a downstream-moving temperature front. In such cases, reactant adsorption tends to moderate and decrease the maximal transient temperature of these fronts. However, when the wrong-way behavior generates an upstream-moving temperature front, reactant adsorption may substantially increase the temperature rise over that attained in its absence and ignite the reactor. Reactant adsorption may also lead to surprising dynamic effects upon changes in feed velocity.
    Additional Material: 13 Ill.
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  • 90
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    AIChE Journal 38 (1992), S. 1631-1638 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Diffusional transport in a network of branching conduits is considered. The branching network is idealized as an ensemble of identical branching segments. Starting with the general species continuity equation, multiscale perturbation analysis is used to derive a one-dimensional, effective transport equation for species concentration. The macrotransport equation contains an effective diffusion coefficient, D*, which arises naturally from the analysis. D* can be computed from a local diffusion problem posed on an individual branching segment of the ensemble network. The local relations defining D* bear clear similarity to their counterparts for transport in spatially periodic porous media. Although this study was originally directed toward describing gas diffusion in the peripheral airspaces of the lung, the results provide insight for other transport processes occurring in branching networks.
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  • 91
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    AIChE Journal 38 (1992), S. 1649-1655 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The study of LeVan et al. (1988) concerning the dynamics of mixed-gas adsorption of components having high concentrations is extended to the case of multicomponent isotherms determined from either ideal or nonideal adsorbed solution theory. A discussion is given of the effect of isotherm properties on the dynamics of isothermal, mixed-gas adsorption when the adsorbate concentrations in the feed gas are large enough so that the interstitial fluid velocity varies significantly along the adsorption front.
    Additional Material: 9 Ill.
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  • 92
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    AIChE Journal 38 (1992), S. 1662-1666 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 3 Ill.
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  • 93
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    AIChE Journal 38 (1992), S. 1671-1674 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 4 Ill.
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  • 94
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    AIChE Journal 38 (1992), S. 1675-1682 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 1 Ill.
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  • 95
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    AIChE Journal 38 (1992), S. 1703-1715 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: One of the limitations of today's knowledge-based (KB) systems for diagnostics and supervision is a lack of adequate temporal reasoning mechanisms. Most of these systems are designed primarily to operate with the current values of the process variables and, sometimes, with their derivatives. Such simple capabilities, however, are not always sufficient to identify some complex dynamic phenomena, which in many cases leave their own unique “stamp” on the process behavior, expressed in the form of characteristic temporal shapes of the related variables. To detect and diagnose adequately the events of interest, the KB system should be able to reason about the temporal shapes of the process variables. Although during manual supervision process operators rely heavily on such characteristic shapes as reliable symptoms of underlying phenomena, their exploitation has not been considered seriously by the designers of KB control systems. We propose a generic methodology for qualitative analysis of the temporal shapes of continuous process variables designed to be embedded into a real-time KB environment. It is applicable to bioprocesses, as well as to other complex dynamic systems.
    Additional Material: 17 Ill.
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  • 96
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    AIChE Journal 38 (1992), S. 1729-1743 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Practical guidelines are required for the design and operation of complicated catalytic packed-bed reactors. Primary among design considerations is the avoidance of operating regions of high parametric sensitivity, in which small changes in operating conditions can lead to thermal runaway in the reactor. Existing criteria for predicting these regions rely on complex mathematical formulations for differential sensitivity between input and output variables. The present work centers on the development of practical design criteria for avoiding reactor instability and temperature sensitivity in multitubular packed-bed reactors. A set of simple guidelines is proposed for the sizing of reactors and proper selection of operating conditions. The implications of these open-loop sensitivities for a controlled reactor are investigated. It is shown through simulation studies that violation of the proposed criteria leads to control problems and difficulty in operating at the design point.
    Additional Material: 10 Ill.
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  • 97
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    AIChE Journal 38 (1992), S. 1751-1760 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The experimental validation of on-line estimation of multiple specific growth rates for the bakers' yeast fed-batch process is presented. Pole placement based parameter estimation combined with an asymptotic biomass observer constitute the basic algorithm. The full process model being ill-conditioned for estimation using the available measured state variables, the use of two partial models related to two different states of the process is suggested. An alternating procedure between two sets of estimation algorithms designed from the partial models is proposed. The performance of the alternating procedure is validated both with simulated and experimental data. The accuracy of the estimates of the three specific growth rates involved in this process is verified according to two criteria based on the respiratory quotient and on the evaluation of the ethanol production/consumption rate.
    Additional Material: 20 Ill.
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  • 98
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    AIChE Journal 38 (1992), S. 1761-1768 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Binary diffusion coefficients of some organic compounds in carbon dioxide at 313.2 K and 16.0/25.0 MPa were measured by using the Taylor-Aris tracer response technique. We propose a new correlation of Schmidt numbers as a function of solvent molar volumes for predicting binary diffusion coefficients in dence CO2 and self-diffusion coefficients of dense CO2. The correlation was also found to be valid for predicting self-diffusion coefficients of dense CH4 at Fv/A* 〈 40 or v2/(ṽ2)0 〉 1.62.
    Additional Material: 7 Ill.
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  • 99
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    AIChE Journal 38 (1992), S. 1825-1834 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Unsteady axial mixing due to addition of a batch of sodium chloride solution at the top of a water-filled tube (2.63 cm i.d.) has been studied by measuring the developing concentration profile and the advancing front with dye added to the brine. Data have also been obtained with added baffle plates, with the use of a viscous aqueous solution, and in smaller diameter (1.48, 1.91 cm) tubes. Results can be approximately correlated by means of a model based on unsteady one-dimensional turbulent dispersion. Laminar flow affects the behavior of the advancing front at which the salt concentration is lowest.
    Additional Material: 12 Ill.
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  • 100
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    AIChE Journal 38 (1992), S. 1816-1824 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The problem of diffusion in pore networks that are close to a percolation threshold is considered. Such networks arise: if the network is poorly connected; if the diffusing molecules are of a comparable size to the pores so that the fraction of the network accessible to the molecules is close to the percolation threshold; and in solids with multimodal pore-size distributions in which the pores belonging to the largest mode form a network close to the percolation threshold. We have investigated diffusion in such networks, using a new method in which the mass balance equations for diffusion on a regular lattice are solved using a Monte Carlo approach, coupled with a renormalized effective medium approximation. The method is accurate both close to and far from the percolation threshold, and is fast enough for routine calculations, such as in catalyst design applications.
    Additional Material: 7 Ill.
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